Bisazo compounds containing anthranilic acid and thiazole moieties

ABSTRACT

The compounds of the formula ##STR1## where Y is hydrogen, chlorine, bromine or nitro, Z is hydrogen, chlorine, bromine, a sulfonic ester group or unsubstituted or substituted sulfamyl, X is --O-- or ##STR2## R is alkylene which may or may not be interrupted by oxygen or ##STR3## m is 0 or 1, p is 1 or 2, R 1  and R 2  independently of one another are each hydrogen, unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl, or aryl, or R 1  and R 2  together with the nitrogen form a heterocyclic structure, R 3  is hydrogen or unsubstituted or substituted alkyl, R 6  and R 7  independently of one another are each hydrogen, unsubstituted or substituted alkyl, alkoxy or acylamino, K is a radical of a coupling component, A⊖ is an anion, R 4  is unsubtituted or substituted alkyl and R 5  is hydrogen or C 1  -C 4  -alkyl, and the radical ##STR4## may furthermore be an unsubstituted or substituted piperazine radical, are useful for dyeing acid-modified fibers, leather and in particular paper.

The present invention relates to compounds of the general formula (I) ##STR5## where Y is hydrogen, chlorine, bromine or nitro, Z is hydrogen, chlorine, bromine, a sulfonic ester group or unsubstituted or substituted sulfamyl, X is --O-- or ##STR6## R is alkylene which may or may not be interrupted by oxygen or ##STR7## m is 0 or 1, p is 1 or 2, R¹ and R² independently of one another are each hydrogen, unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aralkyl or aryl, or R¹ and R² together with the nitrogen form a heterocyclic structure, R³ is hydrogen or unsubstituted or substituted alkyl, R⁶ and R⁷ independently of one another are each hydrogen, unsubstituted or substituted alkyl, alkoxy or acylamino, K is a radical of a coupling component, A⁻ is an anion, R⁴ is unsubstituted or substituted alkyl and R⁵ is hydrogen or C₁ -C₄ -alkyl, and the radical ##STR8## may furthermore be an unsubstituted or substituted piperazine radical.

Specific examples of radical Z in addition to those stated above are SO₂ NH₂, SO₂ NHCH₃, SO₂ NHC₂ H₅, SO₂ NHC₃ H₇, SO₂ NHC₄ H₉, SO₂ NHC₆ H₅, SO₂ N(CH₃)₂, SO₂ N(C₂ H₅)₂, SO₂ N(C₃ H₇)₂, SO₂ N(C₄ H₉)₂, SO₂ NHC₂ H₄ OH, ##STR9## SO₂ N(C₂ H₄ OH)₂, SO₂ OCH₂ CH₂ N(CH₃)₂, SO₂ OC₂ H₄ N(C₂ H₅)₂, SO₂ OC₂ H₄ N(C₄ H₉)₂, ##STR10## SO₂ OCH(CH₃)CH₂ N(CH₃)₂, SO₂ OCH(CH₃)CH₂ N(C₂ H₅)₂, SO₂ OC₄ H₈ N(CH₃)₂ or SO₂ OC₄ H₈ N(C₂ H₅)₂.

Z is particularly preferably hydrogen, chlorine or bromine.

Unsubstituted or substituted alkylene radicals R are of, for example 2 to 10 carbon atoms, C₂ - and C₃ -radicals being preferred.

Specific examples are C₂ H₄, C₃ H₆, ##STR11## C₂ H₄ OC₂ H₄, C₃ H₆ OC₃ H₆, C₃ H₆ OC₂ H₄ OC₃ H₆, C₃ H₆ OC₄ H₈ OC₃ H₆, C₃ H₆ OC₂ H₄ OC₂ H₄ OC₃ H₆, C₂ H₄ NHC₂ H₄, C₂ H₄ NHC₃ H₆, C₃ H₆ NHC₃ H₆, C₃ H₆ NHC₂ H₄ NHC₃ H₆, C₃ H₆ NHC₆ H₁₂ NHC₃ H₆, ##STR12##

R is preferably, for example, C₂ H₄ or CH₂ CH(CH₃).

As a rule, alkyl radicals R¹ and R² are of 1 to 14 carbon atoms and may be substituted by, for example, N-cycloalkylamino, N,N-di-C₁ -C₅ -alkylamino, hydroxyl or C₁ -C₈ -alkoxy. Other examples are allyl, methallyl and C₅ -C₈ -cycloalkyl.

Specific examples of radicals in addition to those stated above are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-amyl, isoamyl, n-hexyl, isohexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, tetradecyl, 2-hydroxyethyl, 2- and 3-hydroxypropyl, hydroxybutyl, cyclopentyl, cyclohexyl and cyclooctyl, N,N-dimethylaminoethyl, N,N-diethylaminoethyl, N,N-dipropylaminoethyl, N,N-dibutylaminoethyl, 3-(N,N-dimethylamino)propyl, 3-(N,N-diethylamino)-propyl, 3-(N,N-dipropylamino)propyl and 3-(N,N-dibutylamino)-propyl, N-cyclohexylaminoethyl 3-N-cyclohexylamino)-propyl, 3-(N-cyclooctylamino)propyl, N-methyl-N-cyclohexylaminoethyl, 3-(N-methyl-N-cyclohexylamino)-propyl, benzyl, phenethyl, phenyl and tolyl.

R¹ and R², together with the nitrogen, can form, for example, the radicals of the following heterocycles: pyrrolidine, piperidine, morpholine, piperazine which may be substituted at the nitrogen by methyl, ethyl, n- or isopropyl, n-, iso- or sec.-butyl, 2-hydroxyethyl, 2-aminoethyl, 2- or 3-hydroxypropyl or 2- or 3-aminopropyl, imidazole which may be substituted in 2- and/or 4-position by methyl, ethyl, propyl or butyl, or N-3-(C₁ -C₁₂)-alkyl or vinylimidazole which may be further substituted in the 2- and/or 4-position by methyl, ethyl, propyl or butyl.

Examples of preferred radicals R¹ and R² are methyl, ethyl, n-propyl, isopropyl, C₂ - and C₃ -hydroxyalkyl or cyclohexyl.

Preferred heterocyclic radicals ##STR13## are, for example, those or morpholine, piperidine, 4-methylpiperazine, 4-ethylpiperazine, 4-hydroxyethylpiperazine, 4-(2'-aminoethyl)-piperazine, imidazole, 2-methylimidazole and 4-methylimidazole.

The radical ##STR14## may furthermore be a group of the formula ##STR15##

Furthermore, examples of suitable radicals R³ are C₁ -C₁₂ -alkyl and C₂ -C₄ -hydroxyalkyl, such as methyl, ethyl, n- and isopropyl, n- and isobutyl, n- and isoamyl, n- and isohexyl, octyl, 2-ethylhexyl, decyl, dodecyl, 2-hydroxyethyl, 2- and 3-hydroxypropyl, hydroxy-butyl, benzyl, CH₂ CH₂ (OH)CH₂ Cl and CH₂ CH(OH)CH₂ OH.

R³ is preferably C₁ -C₄ -alkyl, C₂ -C₄ -hydroxy-alkyl or benzyl, particularly preferably methyl, ethyl or C₂ - or C₃ -hydroxyalkyl.

R₄ is preferably CH₃, C₂ H₅ or C₂ H₄ OH.

The radicals which carry R⁶ and R⁷ can be unsubstituted or substituted naphthylene radicals of the formula II or phenylene radicals of the formula III. ##STR16##

Specific examples are 1,4-naphthylene radicals which may be substituted in the 2-, 5-, 6- or 7-position by hydroxyl or C₁ -C₄ -alkoxy. 1,4-Naphthylene is preferred. Radicals of the formula III are, in particular, the 1,4-phenylene radicals which are monosubstituted or disubstituted by methyl, methoxy, ethoxy or acylamino, where acylamino is, for example, NHCOCH₃, NHCOC₂ H₅, NHCOC₆ H₅, NHCONH₂, NHCON(CH₃)₂ or NHCONHC₆ H₅. NHCOCH₃ and NHCONHC₆ H₅ and the combination CH₃ /OCH₃ are particularly preferred.

Examples of suitable coupling components K are 1,3-thiazoles of the formula IV, pyrazolones of the formula V, mono- and dihydroxybenzenes, alkoxyphenols, pyridines of the formula VI or VII, anilines of the formula VIII and naphthalene derivatives of the formula IX. ##STR17## where, in the formulae, R⁸ is hydrogen, acetyl, benzoyl, or an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, R⁹ and R¹⁰ independently of one another are each hydrogen, unsubstituted or substituted alkyl or cycloalkyl, or together with the nitrogen form a heterocyclic structure, R¹¹ is hydrogen, methyl, carboxyl, C₁ -C₈ -alkoxycarbonyl, unsubstituted or substituted carbamyl or unsubstituted or substituted phenyl, R¹² is hydrogen, alkyl, cycloalkyl, aralkyl or unsubstituted or substituted phenyl or furyl, R¹³ is hydrogen, alkyl, hydroxyl or unsubstituted or substituted amino, R¹⁴ is hydrogen, cyano, acetyl, unsubstituted or substituted carbamyl, unsubstituted or substituted 1-pyridinium or 3-alkyl-1-imidazolium, R¹⁵ is hydroxyl or unsubstituted or substituted amino, R¹⁶ is hydrogen or unsubstituted or substituted alkyl or aryl and R¹⁷ and R¹⁸ independently of one another are each hydrogen, unsubstituted or substituted alkyl or cycloalkyl, or together with the nitrogen form a 5-membered or 6-membered heterocyclic ring, and R⁶ and R⁷ have the stated meanings.

R⁸ is, for example, C₁ -C₄ -alkyl which is unsubstituted or substituted by chlorine, bromine, cyano, hydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylmercapto, phenoxy, sulfophenoxy, phenylmercapto, amino, N-mono- or N,N-di-C₁ -C₄ -alkylamino, phenylamino, sulfophenylamino, C₁ -C₄ -alkanoylamino or sulfoethylamino, or is, for example, vinyl or cyclohexyl, or is, for example, thienyl, thiazolyl or phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, hydroxyl, C₁ -C₄ -alkoxy, β-C₁ -C₄ -alkanoyloxyethoxy, β-cyanoethoxy, β-carboxyethoxy, β-C₁ -C₄ -alkoxycarbonylethoxy, phenoxy, sulfophenoxy, C₁ -C₄ -alkylmercapto, phenylmercapto, amino, β-C₁ -C₄ -alkanoylamino, benzoylamino, C₁ -C₄ -alkylamino or dialkylamino, phenylamino, sulfophenylamino, C₁ -C₄ -alkylsulfonylamino or phenylsulfonylamino.

Specific examples of radicals R⁸ are CH₃, C₂ H₅, CH₂ Cl, CH₂ CN, CH₂ OH, CH₂ --CH₂ Cl, CH₂ --CH₂ OH, CH₂ --CH₂ CN, CH₂ --COOCH₃, CH₂ COOC₂ H₅, --CH₂ OCH₃, --CH₂ OC₂ H₅, CH₂ SCH₃, CH₂ N(CH₃)₂, C₆ H₅ OCH₂, C₆ H₅, ClC₆ H₄, BrC₆ H₄, FC₆ H₄, Cl₂ C₆ H₃, CH₃ C₆ H₄, (CH₃)₂ C₆ H₃, CH₃ OC₆ H₄, C₂ H₅ OC₆ H₄, NCC₂ H₄ OC₆ H₄, CH₃ OOC.C₂ H₄ OC₆ H₄, H₂ NCOC₂ H₄ OC₆ H₄, CH₃ COOC₂ H₄ OC₆ H₄, HOC₂ H₄ OC₆ H₄, HOC₆ H₄, C₆ H₅ OC₆ H₄, CH₃ SC₆ H₄, C₆ H₅ SC₆ H₄, NC--C₂ H₄ SC₆ H₄, CH₃ CONHC₆ H₄, C₂ H₅ CONHC₆ H₄, H₂ N--C₆ H₄, HOC₂ H₄ NHC₆ H₄, (C₂ H₅)₂ NC₆ H₄, CH₃ SO₂ NHC₆ H₄, C₆ H₅ SO₂ NHC₆ H₄, C₆ H₅ NHC₆ H₄, ##STR18##

R⁸ is preferably C₁ -C₄ -alkyl, β-carboxymethyl, or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, C₁ -C₄ -alkoxy, β-cyanoethoxy, β-carboxyethoxy, phenoxy, sulfophenoxy, C₁ -C₄ -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino.

R⁹ and R¹⁰ are each, for example, C₁ -C₈ -alkyl which may be interrupted by oxygen and substituted by hydroxyl, carboxyl, cyano, chlorine, bromine, phenyl, C₁ -C₈ -alkoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoylamino, acetyl, C₁ -C₄ -alkylaminocarbonyloxy, arylaminocarbonyloxy, C₁ -C₄ -alkoxycarbonyloxy or phenoxycarbonyloxy, or are each, for example, allyl, methallyl, propargyl, cyclohexyl, phenyl-C₁ -C₅ -alkyl, or phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, C₁ -C₄ -alkoxy-carbonyl, nitro or C¹ -C₄ -alkanoylamino.

Specific examples of radicals R⁹ and R¹⁰ in addition to those stated above are hydrogen, methyl, ethyl, propyl, butyl, β-hydroxyethyl, β-methoxyethyl, γ-methoxypropyl, β-cyanoethyl, β-carbomethoxyethyl, β-carboethoxyethyl, β-acetoxyethyl, β-ethoxycarbonylethyl, γ-acetylaminopropyl, phenoxycarbonyloxyethyl, phenylaminocarbonyloxyethyl, butylaminocarbonyloxyethyl, benzyl, β-phenethyl, phenyl, sulfophenyl, disulfophenyl, acetylaminophenyl, carboxyphenyl, cyanophenyl, chlorophenyl and sulfethyl.

R⁹ and R¹⁰ together with the nitrogen form, for example, oligomethyleneimino which may or may not be interrupted by O, N or S, eg. pyrrolidino, piperidino, morpholino, piperazino, α-methylpiperazino, hexamethyleneimino or thiomorpholino S-dioxide.

R⁹ and R¹⁰ independently of one another are each preferably C₁ -C₈ -alkyl, C₂ -C₈ -alkyl which is substituted by hydroxyl, carboxyl, hydroxysulfonyl, cyano, phenyl, C₁ -C₈ -alkoxy, phenoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoylamino or C₁ -C₄ -alkoxycarbonyloxy, or allyl or phenyl-C₁ -C₅ -alkyl, or phenyl which is unsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, cyano or carbamyl, and NR⁹ R¹⁰ is preferably pyrrolidino, piperidino, piperazino or morpholino.

Examples of radicals R¹¹ in addition to those stated above are CONH₂, CONHCH₃, CONHC₂ H₅, CONHC₃ H₇, CONHC₄ H₉, CON(CH₃)₂, CON(C₂ H₅)₂, COOCH₃, COOC₂ H₅, COOC₃ H₇, COOC₄ H₉, COOC₈ H₁₇ and COOC₂ H₄ OH.

R¹¹ is preferably CH₃ or phenyl.

R¹² is, for example, C₁ -C₈ -alkyl, cyclohexyl, benzyl, furyl or unsubstituted or substituted phenyl. Specific examples of radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl and phenyl. The phenyl radical may be substituted, for example, as follows: 2-Cl, 3-Cl, 4-Cl, 2-CH₃, 3-CH₃, 4-CH₃, 2-C₂ H₅, 4-NO₂, 3-NO₂, 3-SO₂ NH₂, 4-SO₂ NH₂, 2-CN, 3-CN, 4-CN, 2-Cl, or 6-CH₃.

Where R¹⁵ is OH, R¹² is preferably phenyl which is substituted by methyl, ethyl, methoxy, ethoxy, chlorine or bromine, and, where R¹⁵ is NH₂, R¹² is preferably hydrogen, furyl, benzyl, cyclohexyl, C₁ -C₆ -alkyl or phenyl.

In addition to hydrogen, R¹³ is, for example, ethyl, n- or isopropyl, butyl, pentyl, α-ethylphenyl, phenyl, methylphenyl or, preferably, methyl.

R¹⁴ is preferably cyano.

R¹⁶ is, for example, hydrogen, phenyl, 2-methylphenyl, 4-methylphenyl, 4-ethoxyphenyl, 2-ethylhex-1-yl, cyclohexyl, acetonylcarbonyl, methyl, ethyl, n- or iso- propyl, preferably hydrogen, methyl, ethyl, phenyl or 4-methylphenyl.

The radicals R¹⁷ and R¹⁸ may be identical or different.

Examples of suitable radicals R¹⁷ and R¹⁸, in addition to hydrogen, are the following substituents: alkyl of 1 to 8 carbon atoms, C₂ -C₆ -alkyl which is unsubstituted or substituted by hydroxyl, cyano, alkoxy of 1 to 8 carbon atoms, phenoxy, phenoxyethoxy or benzyloxy, and cyclohexyl, norbornyl, benzyl, phenylethyl, phenylhydroxyethyl, phenylpropyl and phenylbutyl, and polyalkoxyalkyl, hydroxypolyalkoxyalkyl, alkanoyloxyalkyl, alkoxycarbonylalkyl or phenyl which is unsubstituted or substituted by chlorine, methyl, methoxy or ethoxy, and alkanoyl, aralkanoyl, aroyl, alkylsulfonyl or arylsulfonyl.

Specific examples of suitable radicals R¹⁷ and R¹⁸ in addition to those mentioned above are:

1. unsubstituted or substituted alkyl: CH₃, C₂ H₅, n- or i-C₃ H₇, n- or i-C₄ H₉, C₆ H₁₃, ##STR19## CH₂ CH₂ OH, (CH₂)₃ OH, ##STR20## (CH₂)₄ OH, (CH₂)₆ OH, ##STR21## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ OC₂ H₄ OH, (CH₂)₂ CN, (CH₂)₅ CN, (CH₂)₆ CN, (CH₂)₇ CN, (CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ O(CH₂)₂ CN, (CH₂)₂ O(CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅, (CH₂)₃ O(CH₂)₆ OH, (CH₂)₃ OC₂ H₄ OCH(CH₃)₂, (CH₂)₃ OC₂ H₄ OC₄ H₉, ##STR22## (CH₂)₃ OC₂ H₄ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₂ H₄ C₆ H₅, ##STR23## (CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR24## and the corresponding radicals in which two or three of the groups --OC₂ H₄, ##STR25## are present; ##STR26## CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₃ H₇, CH₂ CH₂ OC₄ H₉, CH₂ CH₂ OC₆ H₅, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR27## (CH₂)₃ OC₈ H₁₇, (CH₂)₃ OC₆ H₁₁, (CH₂)₃ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ C₆ H₅, (CH₂)₃ OC₆ H₅, ##STR28##

2. unsubstituted or substituted cyclo- and polycycloalkyl: ##STR29##

3. aralkyl: ##STR30##

4. unsubstituted or substituted phenyl: C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, C₆ H₄ OCH₂ CH₂ OH or C₆ H₄ Cl;

5. CH₂ CH═CH₂, (CH₂)₅ COOCH₃, ##STR31## where n is 2, 3, 4 or 6, C₂ H₄ OCOCH₃, C₂ H₄ OCHO, C₂ H₄ OCOCH₃, (C₂ H₄ O)₂ COCH₃, (C₂ H₄ O)₂ CHO, and (CH₂)₃ OCOCH₃, (CH₂)₃ OCHO;

6. CHO, CH₃ CO, C₂ H₄ CO, C₃ H₇ CO, ##STR32## C₂ H₅ CO, CH₃ C₆ H₄ CO, C₆ H₅ CH₂ CO, C₆ H₅ OCH₂ CO, CH₃ SO₂, C₂ H₅ SO₂, C₆ H₅ SO₂ or CH₃ C₆ H₄ SO₂.

Examples of preferred substituents R¹⁷ and R¹⁸ are hydrogen, CH₃, C₂ H₅, n- or i-C₃ H₇, n- or i-C₄ H_(g), ##STR33## CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₄ H₉, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR34## (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR35## CH₂ C₆ H₅, C₂ H₄ C₆ H₅, and ##STR36## C₆ H₅, C₆ H₄ CH₃, C₆ H₄ OCH₃.

Examples of anions are chloride, bromide, hydrogen sulfate, sulfate, nitrate, phosphate, hydrogenphosphate, dihydrogen phosphate, carbonate, bicarbonate, tetrachlorozincate, aminosulfonate, methylsulfonate, methylsulfate, ethylsulfate, formate, acetate, hydroxyacetate, aminoacetate, methoxyacetate, propionate, lactate, maleate, malonae, citrate, benzoate, phthalate, benzenesulfonate, toluenesulfonate, oleate and dodecylbenzenesulfonate.

The compounds of the formula I can be prepared by diazotizing an amino compound of the formula ##STR37## and reacting the product with a coupling component of the formula

    H--K.

The Examples which follow illustrate the preparation. Parts and percentages are by weight, unless stated otherwise.

The compounds of the formula I are useful for dyeing acid-modified fibers, such as polyacrylonitrile or polyesters, leather and in particular paper. In particular, paper can moreover be printed with printing inks which contain aqueous acidic solutions of I. In the form of bases or salts with fairly long-chain carboxylic or sulfonic acids, such as oleic acid or dodecylbenzenesulfonic acid, they are also suitable, for example, for pastes for ball point pens, solvent dyes or non-aqueous printing inks. With appropriate anions, the dyes are furthermore readily soluble in water and organic solvents, so that they are useful for the preparation of liquid concentrates.

Of particular importance are compounds of the formula (Ia) and (Ib) ##STR38## where Y, A.sup.⊖, m, R to R³ and R⁶ to R¹⁰ have the stated meanings. Y is preferably hydrogen or nitro, R is preferably C₂ H₄, C₃ H₆, --CH(CH₃)CH₂ or C₄ H₈, R¹ and R² are each preferably H, CH₃, C₂ H₅, n-, i-C₃ H₇, n-, i-, sec.-C₄ H₉, C₂ H₄ OCH₃, ##STR39## or cyclohexyl, R³ is CH₃, C₂ H₅ or C₂ H₄ OH, and R⁶ and R⁷ are each preferably H, CH₃ OCH₃ or OC₂ H₅.

R⁸ is preferably C₁ -C₄ -alkyl or β-carboxymethyl or is preferably phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, C₁ -C₄ -alkoxy, β-cyanoethoxy, β-carboxyethoxy, phenoxy, sulfophenoxy, C₁ -C₄ -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino. Phenyl is particularly preferred.

R⁹ and R¹⁰ independently of one another are each preferably C₁ -C₈ -alkyl, or C₂ -C₈ -alkyl which is substituted by hydroxyl, carboxyl, hydroxysulfonyl, cyano, phenyl, C₁ -C₈ -alkoxy, phenoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoylamino or C₁ -C₄ -alkoxycarbonyloxy, or are each preferably allyl, phenyl-C₁ -C₅ -alkyl, or are each preferably phenyl which is unsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, cyano or carbamyl and NR⁹ R¹⁰ is preferably oligomethyleneimino which may or may not be interrupted by O or N. R⁹ and R¹⁰ are each particularly preferably hydrogen, phenyl, methyl, ethyl or propyl, and NR⁹ R¹⁰ is particularly preferably morpholino, piperazino or piperidino.

EXAMPLES Example 1

208 parts of 2'-dimethylaminoethyl anthranilate are stirred with 500 parts of ice. 500 parts of concentrated hydrochloric acid are added, with external cooling, followed by the addition of 300 parts by volume of 23 percent strength aqueous sodium nitrite solution at below 5° C. The mixture is stirred for three hours at 10°-15° C., excess nitrite is destroyed by adding amidosulfonic acid, and a solution of 129 parts of 1-naphthylamine in 250 parts of glacial acetic acid is then added dropwise. The mixture is allowed to reach room temperature overnight, and the product is filtered off under suction and washed with 20 percent strength sodium chloride solution. The filter cake is stirred with 500 parts of ice and 200 parts of concentrated hydrochloric acid. 300 parts by volume of 23 percent strength aqueous sodium nitrite solution are added dropwise, the pH being kept below 1 by adding hydrochloric acid. Stirring is continued for one hour at room temperature, excess nitrite is destroyed, and a solution of 250 parts of 2-diethylamino-4-phenyl-1,3-thiazole in 200 parts of glacial acetic acid is then added dropwise. The pH is brought to about 4.5 by adding sodium acetate, and stirring is continued for two hours, after which the product is filtered off under suction and washed with 20 percent strength aqueous sodium chloride solution, the filter cake is stirred in ammonia water and the product is again filtered off under suction and washed with water. Freeze drying gives 1203 g of the dye of the formula ##STR40## which is contaminated with salt. Melting point: 75° C.; λmax (50 percent strength acetic acid)=584.

The dye can be dissolved in glacial acetic acid and water to give a liquid formulation. It dyes paper stock intense blue in hue No. 13 (Color Index Hue Indication Chart). The waste water is colorless. The colored paper can be bleached with hypochlorite. The fastness to bleeding in aqueous sodium carbonate solution and water is excellent, even in deep hues, and that in aqueous acetic acid is very good.

Other dyes which substantially correspond to the above compound in hue and affinity for paper stock can be prepared by a method similar to that described above.

    ______________________________________                                          ##STR41##                                                                     Example No.  RNR.sup.1 R.sup.2                                                 ______________________________________                                         2            C.sub.2 H.sub.4 N(CH.sub.3).sub.2                                 3            C.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2                          4            C.sub.2 H.sub.4 N(C.sub.3 H.sub.7).sub.2                                        ##STR42##                                                        6            C.sub.2 H.sub.4 N(C.sub.4 H.sub.9).sub.2                          7                                                                                            ##STR43##                                                        8                                                                                            ##STR44##                                                        9            C.sub.2 H.sub.4 NHCH.sub.3                                        10           C.sub.2 H.sub.4 NHC.sub. 2 H.sub.5                                11           C.sub.2 H.sub.4 N (CH.sub.2).sub.5                                12           C.sub.2 H.sub.4 N (CH.sub.2).sub.6                                13                                                                                           ##STR45##                                                        14                                                                                           ##STR46##                                                        15                                                                                           ##STR47##                                                        16                                                                                           ##STR48##                                                        17                                                                                           ##STR49##                                                        18                                                                                           ##STR50##                                                        19           C.sub.2 H.sub.4 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2                20           C.sub.2 H.sub.4 N(C.sub.2 H.sub.4 OC.sub.2 H.sub.5).sub.2         21                                                                                           ##STR51##                                                        22                                                                                           ##STR52##                                                        23                                                                                           ##STR53##                                                        24                                                                                           ##STR54##                                                        25                                                                                           ##STR55##                                                        26                                                                                           ##STR56##                                                        27                                                                                           ##STR57##                                                        28                                                                                           ##STR58##                                                        29                                                                                           ##STR59##                                                        30                                                                                           ##STR60##                                                        31                                                                                           ##STR61##                                                        32                                                                                           ##STR62##                                                        33                                                                                           ##STR63##                                                        34                                                                                           ##STR64##                                                        35                                                                                           ##STR65##                                                        36                                                                                           ##STR66##                                                        37           C.sub.3 H.sub.6 N(CH.sub.3).sub.2                                 38           C.sub.3 H.sub.6 N(C.sub.2 H.sub.5).sub.2                          39                                                                                           ##STR67##                                                        40                                                                                           ##STR68##                                                        41                                                                                           ##STR69##                                                        42                                                                                           ##STR70##                                                        43                                                                                           ##STR71##                                                        44                                                                                           ##STR72##                                                        45                                                                                           ##STR73##                                                        46                                                                                           ##STR74##                                                        47                                                                                           ##STR75##                                                        48           C.sub.4 H.sub.8N(CH.sub.3).sub.2                                  49           C.sub.4 H.sub.8N(C.sub.2 H.sub.5).sub.2                           50           C.sub.4 H.sub.8N(C.sub.3 H.sub.7).sub.2                           51                                                                                           ##STR76##                                                        52                                                                                           ##STR77##                                                        53                                                                                           ##STR78##                                                        ______________________________________                                    

Other dyes which dye paper blue can be prepared from the corresponding halogenated or sulfochlorinated derivatives of isatoic anhydride by a method similar to that described in Example 1.

    ______________________________________                                          ##STR79##                                                                      No.Example                                                                             ##STR80##      Y      Z                                               ______________________________________                                         54      COOC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                          5-Cl   H                                                55                                                                                      ##STR81##     5-Cl   H                                                56      COOC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                          5-Br   H                                                57                                                                                      ##STR82##     5-Br   H                                                58      COOC.sub.2 H.sub. 4 N(CH.sub.3).sub.2                                                         3-Cl   5-Br                                             59      COOC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                          5-Br   3-Cl                                             60      COOC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                          H      5-SO.sub.2 OC.sub.2 H.sub.4 N(CH.sub.3).sub.                                   2                                                ______________________________________                                    

EXAMPLE 61

The diazo component prepared according to Example 1 is distilled. 13 parts of dimethyl sulfate are added dropwise, at 60° C., to 21 parts of the distilled diazo component in 100 parts of toluene, stirring is continued for one hour at this temperature, the mixture is cooled to room temperature and the precipitate is filtered off under suction. When the product has been dried, the diazotization equivalent is 355 g/equivalent (theory: 334 g/equivalent). The compound is of the formula ##STR83##

After diazotization and coupling similarly to Example 1, the solution is rendered alkaline with sodium hydroxide solution, the aqueous phase is decanted from the greasy dye, and the latter is dissolved in aqueous glacial acetic acid. The dye dyes paper stock blue and produces moderate coloration of the waste water. It is of the formula ##STR84##

EXAMPLE 62

21 parts of 2'-dimethylaminoethyl anthranilate are stirred with 50 parts of water and 71 parts of concentrated hydrochloric acid, while cooling with ice. Diazotization is carried out using 35 parts of 23 percent strength aqueous sodium nitrite solution, the mixture is stirred for three hours, and excess nitrite is then destroyed by adding amidosulfonic acid. A solution of 14 parts of 1-naphthylamine in 50 parts of glacial acetic acid is added dropwise, the solution is buffered at pH 3.5 with sodium acetate, and coupling is completed overnight at room temperature. The mixture is then cooled to 0°-5° C., the pH is brought to 0.7 with concentrated hydrochloric acid, diazotization is effected with 35 parts of 23 percent strength aqueous sodium nitrite solution, and the temperature is allowed to increase to 15° C. in the course of three hours. Excess nitrite is destroyed.

Coupling component: 9.8 parts of 3-methylpyrazol-5-one are dissolved in 100 parts of water and 55 parts of 2N sodium hydroxide solution, and oxyethylated fatty amine and ice are added, and precipitation is then effected slowly with 10 percent strength acetic acid.

The diazonium salt solution is run into the suspension of the coupling component, the pH is brought to 3.5 by adding sodium acetate, and the mixture is stirred overnight and filtered under suction. A moist press cake having a water content of about 20% is obtained. The dye is of the formula ##STR85##

From an acidic, aqueous solution, it dyes paper stock reddish brown in a hue between Nos. 7 and 8 (Color Index Hue Indication Chart). The waste water is virtually colorless; λmax (1:1 h₂ O/glacial acetic acid)=488 nm.

The dyes below can be prepared by a method similar to that described in Example 62, using other terminal coupling components.

    ______________________________________                                          ##STR86##                                                                                                     C.I. Hue                                       Example                                                                               K                λ max                                                                           Indication Chart                               ______________________________________                                         63                                                                                     ##STR87##       487     7-8                                            64                                                                                     ##STR88##       495     7-8                                            85                                                                                     ##STR89##       517     11                                             66                                                                                     ##STR90##               35                                             ______________________________________                                    

Compounds having virtually the same color are obtained when the dimethylaminoethyl radical in Examples 62-66 is replaced with the radicals described in Examples 1-53 and 61.

EXAMPLE 67

21 parts of 2'-dimethylaminoethyl anthranilate in 50 parts of water and 71 parts of concentrated hydrochloric acid are stirred, while cooling with ice. Diazotization is carried out using 35 parts of 23 percent strength aqueous sodium nitrite solution, the mixture is stirred for three hours, and excess nitrite is then destroyed by adding amidosulfonic acid. A solution of 13.7 parts of 2-methoxy-5-methylaniline in glacial acetic acid is added, after which the mixture is buffered at pH 3.5 with sodium acetate and stirred overnight. The pH is brought to 0.8 by adding concentrated hydrochloric acid, and the mixture is cooled with ice and diazotized with 35 parts of 23 percent strength sodium nitrite solution for 4 hours at 5° C. Excess nitrite is destroyed, and a solution of 25 parts of 2-diethylamino-4-phenyl-1,3-thiazole and glacial acetic acid is added dropwise. The pH is brought to 3.5 with sodium acetate, and the mixture is stirred overnight and filtered under suction. The moist filter cake contains, in addition to about 30% of water and 6% of sodium chloride, the compound of the formula ##STR91##

From acidic, aqueous solution, it dyes paper stock violet in hue No. 34 (C.I. Hue Indication Chart). The waste water is virtually colorless; λmax (1:1 H₂ O/glacial acetic acid)=541 nm.

The dyes below can be prepared similarly to Example 67, using other terminal coupling components:

    ______________________________________                                          ##STR92##                                                                     Example     K               λ max                                       ______________________________________                                         68                                                                                          ##STR93##      477                                                69                                                                                          ##STR94##      484                                                70                                                                                          ##STR95##      478                                                ______________________________________                                    

Compounds having virtually the same color are obtained when the dimethylamino radical in Examples 67-70 are replaced with the radicals described in Examples 1-53 and 61.

EXAMPLE 71

2 parts of a 10 percent strength solution of the dye from Example 1, containing acetic acid, are added to a suspension of 50 parts of bleached sulfate pulp of about 30° SR in 2000 parts of water at pH 7. The mixture is stirred for 15 minutes at from 20° to 25° C., after which it is diluted with water to a solids content of 0.2%. This suspension is used to produce paper sheets on a laboratory sheet former, and the sheets are dried for 5 minutes at 100° C., blue sheets being obtained. The waste water is colorless, and the fastness to bleeding in water and aqueous sodium carbonate solution is excellent, while that in acetic acid is good.

When the dyes from Examples 2-70 are used, similar coloring results are obtained.

EXAMPLE 72

1.0 part of the product obtained by milling 90% of the dye from Example 1 and 10% of amidosulfonic acid is sprinkled into a stirred suspension of 100 parts of a mixture of 70% of bleached pine sulfate pulp and 30% of bleached birch sulfate pulp in 2000 parts of water, the total stock having an SR value of about 30°. The mixture is stirred for 10 minutes and diluted with water to a solids content of 0.2%, after which paper sheets are produced on a laboratory sheet former and the sheets are dried for 5 minutes at 100° C. The resulting sheets exhibit a uniform blue coloration and possess excellent fastness to bleeding in water. When products obtained by milling the dyes from Examples 2-70 with amidosulfonic acid are used, similar coloring results are obtained.

EXAMPLE 73

An absorptive web of unsized paper is drawn, at 40°-50° C., through a dye solution composed of 0.5 part of the dye from Example 1, 0.5 part of starch, 3 parts of acetic acid and 96 parts of water. The excess dye solution is pressed out between two rollers. The dried paper web is found to have been dyed blue.

The dyes from Examples 2-70 can be used in a similar manner. 

We claim:
 1. A compound of the formula: ##STR96## where Y is hydrogen, chlorine, bromine or nitro;R is C₂ H₄, C₃ H₆, ##STR97## C₂ H₄ OC₂ H₄, C₃ H₆ OC₃ H₆, C₃ H₆ OC₃ H₆, C₃ H₆ OC₄ H₈ OC₃ H₆, C₃ H₆ OC₂ H₄ OC₂ H₄ OC₃ H₆, C₂ H₄ NHC₂ H₄, C₂ H₄ NHC₃ H₆, C₃ H₆ NHC₃ H₆, C₃ H₆ NHC₂ H₄ NHC₃ H₆, C₃ H₆ NHC₆ H₁₂ NHC₃ H₆, ##STR98## m is 0 or 1; R¹ and R² independently of one another are each hydrogen, allyl, methallyl, C₁ -C₁₄ -alkyl, C₁ -C₁₄ -alkenyl, C₅ -C₈ -cycloalkyl, C₁ -C₁₄ -aralkyl, or C₁ -C₁₄ -aryl, unsubstituted or substituted by N-cycloalkylamino, N,N-di-C₁ -C₅ -alkylamino, hydroxyl or C₁ -C₈ -alkoxy, or R¹ and R² together with the nitrogen may form pyrrolidine, piperidine, morpholine, piperazine unsubstituted or substituted at the nitrogen by methyl, ethyl, n- or isopropyl, n-, iso- or sec-butyl, 2-hydroxyethyl, 2-aminoethyl, 2- or 3-hydroxypropyl or 2- or 3-aminopropyl, imidazole unsubstituted or substituted in 2- or 4-position by methyl, ethyl, propyl or butyl, or N-3-(C₁ -C₁₂)-alkyl or vinylimidazole unsubstituted or substituted in the 2- or 4-position by methyl, ethyl, propyl or butyl; R³ is hydrogen, C₁ -C₁₂ -alkyl, or C₂ -C₄ -hydroxyalkyl; R⁶ and R⁷ independently of one another are each hydrogen, hydroxyl, C₁ -C₄ -alkoxy, methyl, NHCOCH₃, NHCOC₂ H₅, NHCOC₆ H₅, NHCONH₂, NHCON(CH₃)₂ or NHCONHC₆ H₅ ; R⁸ is hydrogen, acetyl, benzoyl, C₁ -C₄ -alkyl which is unsubstituted or substituted by chlorine, bromine, cyano, hydroxyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylmercapto, phenoxy, sulfophenoxy, phenylmercapto, amino, N-mono- or N,N-di-C₁ -C₄ -alkylamino, phenylamino, sulfophenylamino, C₁ -C₄ -alkanoylamino sulfoethylamino, vinyl, cyclohexyl, thienyl, thiazolyl, phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, hydroxyl, C₁ -C₄ -alkoxy, β-C₁ -C₄ -alkanoyloxyethoxy, β-cyanoethoxy, β-carboxyethyoxy, β-C₁ -C₄ -alkoxycarbonylethoxy, phenoxy, sulfophenoxy, C₁ -C₄ -alkylmercapto, phenylmercapto, amino, β-C₁ -C₄ -alkanoylamino, benzoylamino, C₁ -C₄ -alkylamino or dialkylamino, phenylamino, sulfophenylamino, C₁ -C₄ -alkylsulfonylamino or phenylsulfonylamino; R⁹ and R¹⁰ independently of one another are each hydrogen, C₁ -C₈ -alkyl which is unsubstituted or substituted by hydroxyl, carboxyl, cyano, chlorine, bromine, phenyl, C₁ -C₈ -alkoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoylamino, acetyl, C₁ -C₄ -alkylaminocarbonyloxy, arylaminocarbonyloxy, C₁ -C₄ -alkoxycarbonyloxy or phenoxycarbonyloxy, or are each, allyl, methallyl, propargyl, cyclohexyl, phenyl-C₁ -C₅ -alkyl, or phenyl which is unsubstituted or substituted by fluorine, chlorine, bromine, C₁ -C₄ -alkoxycarbonyl, nitro or C₁ -C₄ -alkanoylamino; or R⁹ and R¹⁰ together with the nitrogen form pyrrolidino, piperidino, morpholino, piperazino, α-methylpiperazino, hexamethyleneimino or thiomorpholino S-dioxide; and A⁻ is an anion.
 2. A compound according to claim 1, wherein Z is hydrogen, chlorine or bromine.
 3. A compound according to claim 1, wherein R is C₂ H₄ or CH₂ CH(CH₃).
 4. A compound according to claim 1, wherein R¹ and R² are methyl, ethyl, n-propyl, isopropyl, C₂ - and C₃ -hydroxyalkyl or cyclohexyl.
 5. A compound according to claim 1, wherein R¹ and R² together with the nitrogen form morpholine, piperidine, 4-methylpiperazine, 4-ethylpiperazine, 4-hydroxyethylpiperazine, 4-(2'-aminoethyl)-piperazine, imidazole, 2-methylimidazole or 4-methylimidazole.
 6. A compound according to claim 1, wherein R³ is C₁ -C₄ -alkyl, C₂ -C₄ -hydroxyalkyl, or benzyl.
 7. A compound according to claim 1, wherein R³ is methyl, ethyl or C₂ - or C₃ -hydroxyalkyl.
 8. A compound according to claim 1, wherein R⁸ is C₁ -C₄ -alkyl, β-carboxymethyl, or phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, C₁ -C₄ -alkoxy, β-cyanoethoxy, β-carboxyethoxy, phenoxy, sulfophenoxy, C₁ -C₄ -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino.
 9. A compound according to claim 1, wherein R⁹ and R¹⁰ independently of one another are each C₁ -C₈ -alkyl, C₂ -C₈ -alkyl which is substituted by hydroxyl, carboxyl, hydroxysulfonyl, cyano, phenyl, C₁ -C₈ -alkoxy, phenoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoylamino, C₁ -C₄ -alkoxycarbonyloxy, allyl, phenyl-C₁ -C₅ -alkyl, or phenyl which is unsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, cyano or carbamyl.
 10. A compound according to claim 1, wherein R⁹ and R¹⁰ together with the nitrogen form pyrrolidino, piperidino, piperazino or morpholino.
 11. A compound according to claim 1, whereinY is hydrogen or nitro; R is C₂ H₄, C₃ H₆, --CH(CH₃)CH₂ or C₄ H₈ ; R¹ and R² are each H, CH₃, C₂ H₅, n-, i-C₃ H₇, n-, i-, sec-C₄ H₉, C₂ H₄ OCH₃, ##STR99## or cyclohexyl; R³ is CH₃, C₂ H₅ or C₂ H₄ OH; R⁶ and R⁷ are each H, CH₃, OCH₃ or OC₂ H₅ ; R⁸ is C₁ -C₄ -alkyl, β-carboxymethyl or is phenyl which is unsubstituted or substituted by chlorine, bromine, methyl, ethyl, C₁ -C₄ -alkoxy, β-cyanoethoxy, β-carboxyethoxy, phenoxy, sulfophenoxy, C₁ -C₄ -alkanoylamino, phenylamino, sulfophenylamino or sulfoethylamino; R⁹ and R¹⁰ independently of one another are each C₁ -C₈ -alkyl, or C₂ -C₈ -alkyl which is substituted by hydroxyl, carboxyl, hydroxysulfonyl, cyano, phenyl, C₁ -C₈ -alkoxy, phenoxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkanoylamino or C₁ -C₄ -alkoxycarbonyloxy, or are each allyl, phenyl-C₁ -C₅ -alkyl, or are each phenyl which is unsubstituted or substituted by chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, cyano or carbamyl, and NR⁹ R¹⁰ is oligomethyleneimino which may or may not be interrupted by O or N.
 12. A compound according to claim 1, wherein R⁸ is phenyl.
 13. A compound according to claim 1, wherein R⁹ and R¹⁰ are each hydrogen, phenyl, methyl, ethyl or propyl, and NR⁹ R¹⁰ is morpholino, piperazino or piperidino. 